Synthesis of organic compounds



2 Sheets-Sheet 1 Filed Aug. 23. 1944 Aug. 3l, 1948. 1 c, RUBlN 2,448,279

SYNTHESIS OF ORGANIC COMPOUNDS Filed Aug. 23, 1944 2 Sheets-Sheet 2 VI i g3 .f l 1' A fs f A f t I r 70 f n l a f da, 1 7 5l 54/ L v 5/ d r i 2 ,f77

.E L- 6. C

INVENTOR.

Patented Aug. 31, 1948 2,448,279 SYNTHESIS' oF ORGANIC COMPOUNDS Louis C. Rubin, West Caldwell, N. J., assignor to The M. W. Kellogg Company, Jersey City, N. J., a corporation of Delaware Application August 23, 1944, Serial No. 550,799

3 Claims. 1 This invention-relates to an improved metho for hydrogenating carbon oxides to produce hydrocarbons and Aoxygenated organic compounds. The carbon oxides treated include not only carbon monoxide and carbon dioxide but also other organic compounds which contain the carbonyl group, such as ketones, aldehydes, acyl halides, organic acids and their salts and esters, acid anhydrides, amides, etc., and whose reaction with hydrogen to produce other oxygenated compounds and hydrocarbons is promoted by the catalysts and reaction conditions which are eiective to promote the reaction of hydrogen with carbon monoxide or carbon dioxide. r

While the improved process isapplicable-tothe hydrogenation of these compounds of oxygen and carbon, hereafter referred to as carbon'oxiriles,`

to produce both hydrocarbons and ,oxygenated organic compounds, the invention-*is particularly applicable to the large-scale production of hydro- 20 carbons by the hydrogenation of these. carbon" i Y `It.;isan-biectrof'ithlsinvention'to provide an oxides, particularly carbon monoxide.l In reacting a carbon oxide, such 'asrcz'arbonf monoxide, with hydrogen to produc'eja desiredf product it is necessaryY to maintain'the reactionj25- velocity,ifwhile rapidlyremoving -he'at from the zones voff-highest reaction `rateg-in4v the f.catalyst=.

temperature at the level-at which -the reactions leading to the desired productpre'dominate over' collateral reactions which form undesired prod- Such temperature control isextremely i diillcult because the reactions resulting from. the l30 hydrogenation of carbon oxidesare highly ex-` In previous commercial'installations ucts.

othermic. for carrying out these reactinsein the, vapor phase it has been foundnecessaryto. place the catalyst, in the form .of granules ofsubstantial .35;

size, inv elongated tubes or vcases'having` a'small cross-sectional dimension' in order* toy facilitate. ,jf the rapid transfer of the heatoi.reactil i'rr'from1` the centers .of the catalyst massestoacooling j,

" manet-110i" fluid surrounding the tubes cir-case operations the catalyst is placed-outside tubes.'A

through which cooling' iuidfcircul'ates` In -no case, however, has it been feasible-to have any part of the catalyst mass morethan about one half inch from a cooling surface. out the synthesis of hydrocarbonsby tliisvmethod on a commercial scale it is necessary toiprovide f` thousands of such tubes in order,toiobtainthe necessary contact with cooling sili'rftuse,byf'acata.-A lyst body of adequate volume. y f

are passed over the catalyst `at a low space velocity or in a state of dilution and at a relatively low rea-ction temperature in order to build uprfon thel A catalyst a deposit comprising hydrocarbons "and other organic compounds. Itis only after 4such preliminary conditioning of thev catalystthat itis, possible to pass .the reactantsvata reasonably j 4 high space velocity through thecatalystzoneat Incarrying 45 tainedy suilciently` lovv'A to maintain the greater Under such conditions it is"necessary alsplto subject the catalysts to an extendedprelininary. conditioning treatment in which'the reactants',

. highly hibulentfmotion`` oigtheparticles, whereby --.thyf-circulate Vvaia .high .frateiftliroughout the tense reactivity which would produce heat at a rate in excess of the capacity of the apparatus to withdraw it from such local zones.

Even after the' preliminary conditioning treatment themaximum permissible space velocity of the reactants th'roughthe catalyst zone is limited by the capacity of the reaction apparatus to withdrawv heat from .thereaction zone. The capacity ofthe apparatus is thus` limited' by the necessity for avoiding in anypart of the reaction rzonefareaotionrate which would produce heat in excess ofthe capacity of .theapparatus for withdrawingheat'from such part at a rate of `withdrawal eiiect-ive tci'vriiaintairrv the 'temperailllpiovedl method-"forreacting hydrogen with car- 'fbongoxldesgIinwhich the catalyst 'is employed in f a higlily'eillclent manner," -andj at fa". high space chamber..

gaseous' or `vapor-ous lreactants Awith ilnely divided catalyst. underl conditions such that the catalyst ticlescirculateg-at ahighrate tcp'iodu'ce intimate.

Aheat 'ot-:reactiontofcontrol the reaction tempera-t f l.

yt1.ire',by nject'ing-intothe,denseimass.of circula't-v ing',c`atalyst liqiuds-Which are vaporizable 'at' the L ,e'actionbnditio'ns of 'temperaturefand' pressure.

The-"mass otcontactmaterial isfcoritained ina f suitaliilel reactorfyandthe reaction gas mixture is ,passed upwardly through-themass `at a velocity .whichis suiiiciently hightofma'intain the mass of contact'mat'erial Asubstantially'in suspension in the gas.` \.-The velocity of the` gas stream is mainpart of .the catalyst/ masslin pseudo-liquid conditiQnyQinf-zwhich-lit exhibits lmany of.' the properties .of a truegliquid, particularly as tpfowability and density. Atthe same time the velocity is maintainedsufciently high,"in thepreierred form of ,the inventiomto produce in tlfie relatively dense pseudo-lliquid: mass of finely divided material a :The ijlui'cliz df'mass-"fof catalystjis cuite' dense, -'.-resembling 1n'this respect a settledmas'softhe samematerial. I .The density of the uidized`-mass ordinarilyzisl not less than; half that-of the settled While-the 'dense turbulent catalyst mass is said to be suspended in the gas stream, this does not imply any movement of the catalyst mass as a whole along the path of flow of the gas stream. The catalyst mass is suspended in the gas stream but not entrained therein, although a portion o! the catalyst may be carried away from the dense fiuidized mass by becoming entrained in the gas stream emerging from the dense pseudo-liquid catalyst mass.

The gas mixture is introduced into the reactor through an inlet in the bottom of the reactor whereby the gas stream passes upwardly through the catalyst mass to be maintained in a iiuidized condition. Conveniently the inlet comprises one or more connections whose aggregate cross-sectional area is substantially lessthan the corresponding dimension of the space in which the iiuidized mass of catalyst is to be maintained. The gas stream thus passes into the reactor at a relatively high volocity which prevents the passage of catalyst out of the reactor against the enterinar gas stream. Insidethe reactor the velocity of the gas stream decreases to the rate y necessary to produce the .desired degree of iluidization of the catalyst mass. venience the velocity of the gas stream in the reactor is given in terms of the theoretical velocity of the gas stieam through an empty reactor, referred to hereafter as the superficial velocity. It is evident. however, that the velocity of the gas stream decreases to the lsuperiicial velocity only if the reactor is suiliciently larger than the volume of tluidized catalyst to permit the maximum possible disengagement of the gas stream and catalyst. As the concentration of catalyst in the uidized mass varies from a maximum at the bottom to a minimum at the top the linear velocity of the gas stream would normally decrease as it passes upwardly through the catalyst mass even without reaction. The extent of the variation in the density of the iiuidized mass is affected by the superficial velocity, the greatest variation in the density of the catalyst mass being observed at relatively high superficial velocity. The linear velocity of the gas stream is affected also by the contraction in volume of reactants as the reaction proceeds and by the expansion of vaporizing cooling liquids. Thus the superficial velocity at the top of the reactor may be greater or less than at the bottom.

If the catalyst chamber or reactor is somewhat larger than the volume occupied by the fludized mass, the catalyst in the reactor appears to be distributed in two visually distinct phases. The first of these is the relatively dense, pseudoliquid mass of fluidized catalyst, previously described, which occupies the lower portion of the reactor and comprises all but a minor proportion of the catalyst in the reactor. This phase is designated as the dense phase. The second phase, which occupies the upper part of the reactor, is a diffuse phase in which the concentration of contact material is far less. and of a different order of magnitude, than the average concentration in the dense phase. The 'diffuse phase may be said to be a disengaging zone in which the solids lifted above the dense phase by the gas stream are disengaged therefrom to the extent that such solids are present in excess of the carrying 4capacity of the gas stream at the minimum velocity reached by the gas stream in the reactor. In the diffuse phase, the concentration of catalyst material in the gas stream decreases as the latter iiows upwardly For conity. Between the dense phase of high concentration and the diffuse phase of low concentration there is a relatively narrow zone in which the concentration of solids changes in a short space from the high concentration of the dense phase to the low concentration of the difluse phase. This zone has the appearance of an interface between two visually distinct phases.

While the invention includes within its scope operations involving contact material having sufiiciently large particle size such that substantially no part of the contact material is carried by entrainment in the gas stream at the superficial velocity the preferred method of operation involves ordinarily the use of contact material and operating conditions such that a portion of the contact material is carried by entrainment in the gas stream at the supercial velocity. This results from the fact that nely divided contact materials are desirable as presenting a greater ratio of surface to volume and aiording themaximum efficiency of heat transfer between particles 'and the further fact that sufllcient mixing of a catalyst mass of substantial cross-sectional area ordinarily requires the use of superilcial velocities which entrain a portion of the iinely divided contact material in the gas stream. In this preferred method of operation mere settling is not suicient to disengage al1 the catalyst from the gas stream emerging from the dense phase of the catalyst mass. Hence it is necessary to provide means in the reactor to separate entrained catalyst from the gas stream or replenish the catalyst mass by intermittent or continuous addition of iinely divided catalyst to the reactor. Catalyst to be added to the suspended mass may be entrained in the entering gas stream and thus carried into the reactor or it may be added directly to the reactor at a point above the gas inlet. The catalyst thus charged to the reactor may comprise fresh contact material or catalyst previously carried out of the reactor by entrainment. Catalyst thus recovered and returned may be subjected to any appropriate treatment after recovery, such as cooling and reviviiication.

The gas stream'is withdrawn from the top of the reactor through an exit whichis ordinarily 'of substantially smaller cross-sectional area than the reactor. .This provides a high velocity outlet for the gases which is surrounded by an area in Whichthe gas velocity accelerates. The nearer this zone of accelerating gas velocity is to the dense phase, the greater is the concentration of solids in the gas stream entering the zone and thegreater is the quantity of solids which must be recovered from the exit stream or separated by means in the reactor. The quantity .approaches the carrying capacity of the high velocity exit gas stream when it is desired to maintain the upper level of the dense phase in the vicinity of the zone'of accelerating velocity.

In the preferred method of operation the reactor is made sufilciently larger than the required volume of dense iiuidized catalyst mass to provide a relatively largediffuse phase in which substantial disengagement of catalyst from the gas stream occurs by mere settling. The residual amount of catalyst still carried by entrainment is recovered from the gas stream outside the reactor, or separating means are provided in the reactor.

The operation is initiated by charging the re- 'theA i catalyst is Yeiected:'- t necessary to-,fconce'ntrate v u thatfporti'onoi the' dense lphase inf which the reactor with a quantity of catalytic material which it is expected will be uivalent to the mass of catalyst maintained in the reactor in the dense phase. Thereafter, the passage of the gas stream through the reactor and upwardly through the catalyst mass is initiated at the velocity which fluidizes the mass, i. e., converts it to the relatively dense pseudo-liquid condition involving highly turbulent motion of the particles. At the same time if necessary there is commenced the addition of finely divided catalyst material to the reactor at a rate equivalent to the withdrawal of catalyst from the reactor in the gas stream by.en trainment. Alternatively the highly turbulent dense pseudo-liquid phase may be established in the reactor initially by flowing the gas stream through a substantially empty reactor and charging the nely dividedsolici contact material int-o the reactor at a rate greater than the carrying capacity of the gas stream at the superficial velocity imposed by the dimensions of-the reactor. As a result of this excess loading of the gas stream the desired dense phase is gradually built4 up in the reactor. -When the height of. the dense phase in thereactorl is suflicient toproduce thecatalyst volume equivalent to the necessaryspace velocity;

ofthe reactants intheireaction zone'theV rate at which solids are introduced into -the reactor is adjusted to correspond: tothe rate of withdrawal by entrainmcnt.'` i

Inv accordance with this invention 'the turbulent mass vof `suspended catalyst inthe densephaseis1 f least -a substanti al apropor maintained at the desired `reactior'i temperatur'ef level by directly, injecting ,into the dense? phase liquids which areryaporizable at the reaction-,con,

ditions ofit'emperaturerpressure and concentra@ tion.` The quantity of 'suchfinjected 'liquids rand i the distribution" thereof in the-reaction zone are controlled-to produce substantially instantaneous vaporization Aof .the liquids-whereby vthe forma;A

tion of 'agglomerates in the.'v catalyst mass .is avoided. In operations -which f produce a high degree ofturbi'ile'nce in the catalystmass whereby the eatalyst'p'articies circulate-ata 'relatively high tialiy' anyv partjorthe dens-phase frfifth'e edn-- promote thereaction' `of"l oxides and which can beditions of operations are-.suc thatcirculation of"y sser degree it is rated from the reaction. products externally oct the reactor. Y

nieuwe liquids ini While kieselguhr has. beeniyigoun Asupport in previousprocesses-invul In this improved metho'djfof opera-tio'njtfhere Vis l.

no necessity for removingcatal-yst material-.trom

the reactor in excess ofl the-quantity which it may be desired t'o--remove for revi'vlcation treatment or for 'the removal of 'waxyr products therefrom.,` :It

is desirable, therefore, tti-maintain. a` relatively large disengi'igir-ig l.space' a.b ove-thev ldense phase in the reactor 'topermit substantial; separation vof entrained Contact Y inagter ia,l'iirciniv the* gas str eain, inthe reactor.; The-amount .carried Voverheadby '-,iiajct material-consist off pa ic 4,tlingfrate is less, thantli ',the,- reactor whereby the tactiiriaterial may consi L condition suitable for the vthe catalyst is' to be vampie maybe employed. For .inertmaterials may perature in the reaction zone necessarily is one which is completely vaporized at the reaction conditions of temperature, pressure and concentration. The simplest and most available liquid for this purpose is water but the use of water may be undesirable in some instances because of an adverse effect on the catalyst mass by the water. Preferably the cooling liquid should be non-reactive with the catalyst and for this reason it is satisfactory ordinarily to employ a portion of the liquid product of the process, particularly when such liquid product is in a highly saturated condition. For example, in the hydrogenaw tion of carbon monoxide to produce a hydrocarbonv mixture a light naphtha'produced in the process may be employed as the coolingliquid. This material is then recovered in the product recovery system and returnedfor reuse.' ,Instead of the light naphtha a higher,;o' 11 lower, b oiling fraction may be employed.- Alternatively,similari materials obtainedv from any. source may be employed. In the selection-jota coolingiiquidfrom an external source it is necessary.' to avoid the introduction of deleterious compounds; siichas sul-A phur compounds, whichf--maysinjure'thecatalyst. For this reason a liquidproducedgfin th'v highly desirable as the coolingdiu' tion in the dense phase i t entramedi in` theV .gas stre mixture'of particles 'varying 400 microns (average 'd ia bel mieli;` mass. Y. The catalysts employe process. Cobalt. nickeLand suitable supports and p roo'te tion it now appears thatelays re 'superiorin--the the .properties 'desired'-in'fftheproduct;

hydrogenation of carbon monoxide; the kli 'een #and 'carbon monoxide may @bef'chargeditqft e rc'-v l the variations discussed above; and :meg-*catalyst withdrawn from :thefreactor-j-Ior rev-ivificatibirg'r.

"employedf waxvrecovery may beremoved`directlyfrom 4the x densefphasef'at ail'ower point'in-the reactor. The liquid;Which-is-inictedttoi-control theA tem. 'j-A actor in ratiosv which have been-found satisfactory Y The operatingcondtionsare'generallyjsimilar to Athose employed in .previous fixed -`b elcl.. )pera tions.'j V"Ihe'gasstream maybe passed-through the j reactor at a superficial space velocity of 10o-1000 volumes (measured at standard conditions of temperature and pressure) of gas per hour per volume of fluidized dense catalyst phase. The temperature employed is aected largely by the nature of the catalyst. Cobalt and nickel catalysts usually are employed at o-400 F. while iron catalysts require temperatures of o-600 F. The pressure employed may vary from atmospheric to superatmospheric pressures which do not produce condensation in the reactor.

The invention will be described in more detail by reference to the accompanying drawings and by reference to specific operations embodying the invention. In the drawings Fig. 1 is a diagrammatic representation of apparatus for carrying out the invention and Fig.'2 is a view in elevation, partly in section, of the reactor employed in the specific operations which are described.

Referring to Fig. 1 the reactor I0 is provided witha quantity of powdered catalyst which, upon being iiuidized by the passage of reacting vapors upwardly therethrough, forms a pseudo-liquid dense phase in the lower part of the reactor, The charge gas comprising, for example, hydrogen and carbon monoxide and in a usual ratio, is introduced into the lower part of reactor I0 through line Il which is provided with a compressor I2. The dimensions of reactor I0 and the quantity of catalyst are regulated whereby the suspension of the catalytic contact material in the stream of gas introduced through line II lil) produces a dense phase whose upper surface is suiilciently low to leave a substantial disengaging space above the dense phase. The upper level of the dense phase, that is. the interface between the dense phase and the diffuse phase in reactor In is indicated at I3. In accordance with the preferred method of operating the invention a substantial separation of entrained catalyst occurs in the area above the dense phase whereby the quantity of catalyst carried from the reactor in the high velocity exit stream is restricted to a minimum. The high velocity exit of the gas is provided by line I4 which connects at one end with the upper part of reactor I0 and leads to suitable separating means such as a cyclone separator I5. v

I'he reacting gases enter reactor I0 through line Il at a high velocity such that the finelyv divided catalytic material in reactor I0 does not pass downwardly from reactor I0 into line II. The initial charge of catalyst or make-up catalyst may be introduced into reactor I0 by entraining it in the gas stream in line II, from line IIa; As the reactants enter reactor I0 from line II there is a substantial decrease in the upward velocity of the gases. The rate at which the reactants are charged to reactor I0 is regulated to provide in reactor I Il an upward velocity which suspends the catalyst mass in the gas stream and provides a high degree of mixing of the catalyst mass whereby catalyst particles circulate throughout the dense phase. The vaporous reactants may be introduced through line II into reactor I0 at a relatively low temperature whereby they are heated to the reaction temperature by contact with the hot catalyst which is circulating in reactor Ill. In initiating the operation the catalyst may be brought to the reaction temperature by temporarily preheating the charge gas. as by the provision of heating means I6. After the initiation of the reaction, preheating of the charge gas at Ii may be unnecessary and even undesirable.

As the reactants and reaction products emerge from the dense phase at the interface I3 they pass upwardly through the remainder of reactor Ill at a still lower velocity in which entrained catalyst is separated out of the gasstream. Preferably the height of the reactor is suicient to permit disengagement of entrained catalyst to the point where the concentration of catalyst in the gas stream is reduced to an amount of the order of magnitude of the carrying capacity of the gas stream at the superficial velocity.

The mixture of reactants, reaction products and remaining entrained catalyst passes through line I4 into the cyclone separator I5 in which a substantial proportion of the entrained catalyst is separated. The catalyst thus separated at I5 is returned directly to reactor Ill by means of a suitable dip-leg I1 which extends downwardly into the reactor to a point below interface I3. Preferably the lower end of dip-leg Il is turned up as shown to minimize the passage of reacting gases into dip-leg I '1. The catalyst flowing downwardly in dip-leg I1 may be aerated if necessary by the injection of inert gases such as steam by means not shown.

The gas stream emerges from separator I5 through line I8 which connects with a second catalyst separator I9 similar in construction and arrangement to separator I5. In separator I9 a further separation of entrained catalysts is effected and solids thus separated are returned to reactor I0 through dip-leg 20.

As the reaction of hydrogen and carbon oxide is highly exothermic and as it is necessary to maintain the reaction zone, that is the dense catalyst phase below interface I3, at the temperature level which promotes the formation of the desired product, it is necessary to remove the heat of reaction from the reaction zone as it is developed. In accordance with this invention the removal of heat from the reaction zone is effected by the injection of liquids which are vaporized by the heat of reaction; This provides for substantially uniform temperature conditions throughout the dense phase which constitutes the reaction zone because the high rate of circulation of catalyst in the dense phase permits effective heat exchange between hot catalyst particles and particles which have been cooled by evaporating liquid.

In accordance with the preferred modification of this invention a relatively light oil produced in the process is employed as the cooling fluid. It will be understood, however, that this is primarily for convenience since a suitable liquid from any source may be employed. Such a liquid is supplied from the system through line 2I which connects with a distributing header 22. As the reaction is most intense near the entrance of the reactants the development of heat by the reaction occurs largely in the lower part of the dense phase. Consequently header 22 is located at or near the place in the lower part of the dense phase at which production of heat is greatest. However, it may be desirable to introduce cooling liquid at a higher point in the dense phase instead of, or in addition to, the introduction of liquid in the lower part of the dense phase. For example, a branch line 23 may be provided to connect line 2l with a distributing header 24 located in the upper part of the dense phase. It may be preferable to introduce the cooling liquid at 24 in order to avoid any suppression of the reaction which might occur through over cooling the catalyst particles in the zone of greatest reaction rate. Alternatively all or a part of the cooling liquid may be introduced through a suitable spray header 25 which is located above the dense phase. Header 25 is connected with line 2| by means of suitable branch line 25a.

The quantity of cooling liquid introduced through headers 22, 24 and 25 is regulated to the amount which will evaporate completely in the reaction zone. yPreferably also the liquid employed is one which vaporizes readily at the reaction conditions whereby the time of residence of liquid .in contact with the catalyst mass is limited. In this manner agglomeration of 'the cat'- alyst particles is avoided. The vaporized cooling liquid passes overhead with the gas stream flowing through line |4.

The gas stream comprising unreacted gases, vaporous and gaseous products and vaporized cooling liquid together with any residual quantity of entrained catalysts-hows from separator I9 through line 26 which connects with the lower part of a combined catalyst scrubbing and frac-v tionating tower 21. Tower 21 is divided -by a trap-out tray 2li-into upper and lower-sections.

- The lower section is operated primarily'for the removal of entrained catalyst and condensationof heavy oil constituents ci theproduct. vWhile v which heats the condensate collected thereon sufciently to strip gasoline constituents therefrom. It the heating provided by this means is insuilicient suitable heating coils or reboiling means may be provided on tray 28.

'I'he uncondensed gases separated at 36 are withdrawn through line 39 which connects with the bottom of an absorber 40. In absorber 40 the gas stream is contacted withadescending stream of a hydrocarbon oil absorbent. This oil may be any suitable hydrocarbon oil such as a product of the process of the nature of a gas oil or heavy naphtha. This operation serves to scrub from the gas stream remaining light hydrocarbons which it is desired `to include in the liquid prodduct. The scrubbed gases are withdrawn from absorber 40 through line 4|. The enriched absorbent is withdrawn from the bottom of absorber 40 through line 42 vwhich connects with the topy of a stripping tower 43. The enriched absorbent may be preheated during its passage through line 42 by heatexchange with lean absorbent at 44 and lby-special heating means 45. In stripping tower 43 the enriched absorbent is further heated some fractionation-may -be eiected the bailies 28 are arranged primarily to effect-intimate. com.- tact of gases lwith a circulating. liquid.. stream which flows downwardly over' the battles Vinicon-f; tact with the upwardly rising columnof gas.V Inf this manner entrained catalyst is separated"from,

the gas stream by condensation `ofwliqilids in the gas streamfand' by the scrubbing action of the circulating stream of liquid. The slurry which forms is recirculatedy from the bottomof tower 21 through line 39 to a point in tinlver21justA below tray 28. Condensation and fractionation is afforded by heating the slurry in the" Ibottom of tower 21 by heating means 3| and'iby cooling at 32 the stream of liquidy circulating throughline 30. A pump 33 is provided in line 30 to circulate the slurry. n 4 In the upper part'of tower 21 temperature conditions are regulated 'to ei ect separation vof a condensate consisting of the liquid productboiling.

nabove the gasoline boiling range.

Suitable gas and liquid contact means lare vprovided to assist fractionation. :The condensate collects on trap- I out tray.28 and vis withdrawn as a product of the process through line'34. This product yis designated foridentiflcation as a gas oil but it is understood that Aits boiling characteristics are aiected by the amount of the oil product which is separated as a condensate below tray 28. It will be understood furthermore that the separation of this fraction is merely illustrative of the recovery of an intermediate liquid product."

It is evident that meansmay be 'provided for iractionatingA the' liquid product into any desired number of fractions. A w The uncondensed'gas'es and vaporspass overhead from tower 21 through line 35 whichvcon-l vnects with a separator 36. The gasesandvapors passing through 1i`ne35 are cooled .at 31 sumci'ently to effect substantial condensation of theliq'uids by the application of heat at 46 in the bottom of tower 43 sufciently to vaporize the light hydrocarbons absorbed in tower 40. Suitable gas and .liquid contactv means are provided in tower 43 to assist in thev separation of the absorbed hydrocarbonsand vthe absorbent. The stripped absorbent is returned to tower through line 42a,

b y pump 43a', "during which passage it is cooled --at 44'and45a. The vaporized light hydrocarbons vpass 4overhead from tower 43 through line 41 through'which. they are returned to separator 36 by means .of compressor 48. Substantially l, complete condensation of these hydrocarbons is eected by cooling at 49.

I -The condensate accumulated in separator 36 may be withdrawn as a product of the process .through -line 50 provided with a pump 5|. In accordancewith one modification of the invention this oil may be employed as the cooling fluid in reactor 0. For this operation line 2l is connected with line 50 as shown and a portion of the oil flowing through line 50 is diverted for injection into reactor I0 in the manner described above..

The slurry which is circulated through the lower portion of tower 21 and line 30 continuously receives accretion of oil and catalyst from the incomingreaction product. Consequently a portion of this slurry is diverted from line 30 through line 52 and passed to a settler'. 53.. In settler 53 the slurry is treated to separate the greater part of the oil from the solid catalytic material. The oil is separately withdrawn from settler v53 through line 54 as a product of the process. drawn yfrom settler 53 through line 55 in which it. 60.

The separated solid catalyst is withis mixed with light oil to form a slurry. Oil for l51 into reactor vlll in a suitable point. In this A.manner the catalyst separated at v53' is returned .to the reaction zone for further use, as a slurry and higher boiling Agases such 'as those havingfj I e ordinarily injected into reactor I0 as a cooling Vin -whic'hfthe vehicle is a portion ofthe light oil fluid. Trie-liquidv componentlof the' slurry intro- 'duced-.in'toffreactor l0 through line 55 is quickly .fvaporized and the solid component of the slurry -i's converted-toits former condition as a substan- '-.tially dry" catalytic material which is readily .dispersed in the densephase o f the catalyst zone @reactor 1.0#

A and 2i.

While the liquid product -of the process'recovered at 58 is entirely suitable for use as the cooling fluid and for reslurrying the recovered catalyst it will be understood that these functions may be performed by the same or diierent liquids obtained from an external source. The sole requirement of the cooling fluid is that it shall be readily vaporized at the reaction temperature whereby agglomeration of the catalyst particles is avoided. Instead of employing the wide boiling fraction represented by the product recovered at 50 it may be desirable to employ a relatively narrow boiling fraction obtained as a product of the process.

To obtain such a narrow boiling fraction the liquid product owing through line 58 may be diverted through line 58 into a debutanizer tower 59. In tower 59 conditions of temperature and pressure are regulated to separate a bottom product comprising a debutanized gasoline which is withdrawn throughlline 68, and an overhead prod-- uct consisting essentially of light hydrocarbons having three and four carbon atoms per `molecule. An intermediate fraction of relatively narrow boiling range is separated as a liquid condensate on trap-out tray 6I which is located at a suitable point in tower 59 above-the charge point. The condensate thus separated is withdrawn through line 82 which connects with line 58 in the manner shown for passage into lines 58 Cooling means 83 may be provided in line 58 as shown to precool the cooling liquid to any desired temperature.

The gases passing overhead in tower 59 are withdrawn through line 84 which connects with reux drum 95. Cooling means are provided at 88 to effect substantially complete condensation of the gases. The condensate thus obtained is separated in drum 85 and a portion is returned to tower 59 as reflux through line 51, the remainder being withdrawn as a product of the process through line 88. Uncondensed gases separated at drum 95 may be passed to absorber 48 through line 59 which connects drum 85 with line 39.

Instead of the relatively light oils in lines 58 and 62 a. heavier oil such as the gas oil in line 34 or the oil in line 54 may b e employed, by means of suitable connections, not shown, as the cooling oil. y

The invention will be described in further detail by reference to specific operations carried out in the small scale reactor illustrated in Fig. 2. In Fig. 2 the apparatus is shown in four sections which are joined at AA, B-B and CC. The apparatus of Fig. 2 consists essentially of three parts, which are a reactor 18, a shell 1| enclosing reactor 18, and catalyst filter means 12 which surmounts reactor-18. Reactor 18 is an elongated cylinder connected to a high velocity inlet pipe 13 by means of conical member 14. Jacket 1|, which extends from a point near the top of reactor 18 to a point sufciently low to enclose a substantial length of pipe 13, is adapted to contain a body of liquid, such as water, or Dowtherm. This temperature control liquid is main- The remaining portion of the apparatus of Fig. 2, located above reactor 18 and in communication therewith, is the catalyst filter means 12 which is provided to separate catalyst which is carried upwardly out of the dense phase in reactor 18. The upper end of reactor 10 is connected by a conical member 18 with an enlarged conduit 11. This provided for an enlargement of the path of flow of the gas stream emerging from the reactor, with a corresponding decrease in.

upward velocity whereby partial disengagement of solids from the gas stream is eiected. Conduit 11 is connected by a manifold 18 with conduits 19 and 80, which are similar in construction and diameter to conduit 11. Each of conduits 19 and 88 is provided with an internal filter which is illustrated at 9| in the portion of conduit 88 shown in section. Filter 8i is constructed of porous material which is permeable to the gases and vapors passing from reactor 18 but impermeable to solids carried by entrainment therein. Filter 8| is cylindrical in shape and closed at the bottom end. It is dimensioned in relation to conduit 88 to provide a substantial annular space between the outside of filter 8i and the outside wall of conduit 88 for the passage of gases and entrained catalyst upwardly about the outer surface of filter 8i. The upper end of filter 8i is mounted in closure means 82 in a manner whereby the gases and vapors from reactor 18 must pass through filter 9i to reach the exit pipe 83. A similar filter is similarly arranged in conduit 19.

The principal parts of the apparatus of Fig. 2, aside from filters, are constructed of extra heavy steel pipe. Reactor 18 comprises a 153 inch length of extra heavy 2 inch steel pipe having an inside diameter of 1.94 inches and an outside diameter of 2.38 inches. Pipe 13 comprises extra heavy half inch steel pipe having an inside diameter of 0.55 inch, approximately 5 inches of this pipe being enclosed by jacket 1I. The conical member 14l is approximately 3 inches long. Jacket V1I comprises a length of extra heavy 4 inch steel pipe having an inside diameter of 3.83 inches. Pipe 15 consists of extra heavy 2 inch steel pipe. The ends of jacket 1i are formed by closing the ends of the 4 inch steel pipe in any suitable manner as shown. Conduits 11, 19 and 88 and manifold 18 are formed of extra heavy 6v inch steel pipe having an inside diameter of 5.76 inches. The total length of the filter assembly represented by these conduits and member 16 is 61 inches. The'filter 8i is approximately 3 feet long and approximately 41/2 inches in outside diameter, the walls of the filter being approximately 3A of an inch thick. The high velocity outlet at 83 is provided by more extra heavy half inch steel pipe.

The injection of cooling fluids into reactor 18 is provided for by nozzles 84, 85 and 86, which are located 18, 66 and 120 inches, respectively, above the lower end of reactor 18, which is the juncture between rca-:tor 10 and conical member 14. Nozzles 84, 85 and 88 consist of steel tubing having an inside diameter of approximately 0.3 inch and have an orifice of about l/ of an inch in diameter.

The catalyst filter means provided by filter 8| and the corresponding element in conduit 19 provide substantially complete separation of entrained finely divided catalytic material from the outgoing stream of vapors and gases. The filters in conduits 19 and 88 are employed alternately during the operation so that the stream of gases 'andere and vapors and entrained solids pass from conduit 11 through manifold 1l into one or the other of conduits 'I9 and Il. The filter which is n ot in use is at the same time subjected `to a treatment designed to dislodge solids which have accumulated on the outer surface of the nlter during the previous period of use. This treatment comprises iiowing a gas streaminwardly through the usual exit pipe and through the filter in the reverse of the usual direction. The gas stream employed for this purpose ilows out'oi' the illter into the conduit and downwardly into manifold 1l. At that point the downflowing gas combines with the upowing stream of reactants from conduit 1l and the combined stream passes upwardly into contact with the illter in use. Any substantially inert gas may beemployed for blowing back the filter but it is convenient to employ a portion of the uncondensed end gas from the process.

In the operation of the apparatus of Fig. 2 the desired quantity of nely divided solid catalyst is introduced into reactor through a suitable connection, not shown, to conduit 11. The catalyst preferably is preheated to the reaction temperature prior to the contact of reactants therewith. This may be accomplished by heating the temperature control fluid in jacket 1i to the desired temperature or by passing hot inert gas through reactor 10. Alternately the catalyst may be given the final reducing treatment after introduction thereof into the reactor by the passage of hot hydrogen thereover. This is sumcient to preheat the catalyst.

The reacting gases may be introduced through pipe 13 at the reaction temperature or at room' temperature or at higher or lower temperatures. If the reactants flow through 'pipe l13 at a temperature lower than the reaction temperature they are preheated ordinarily prior to actual contact with the catalyst to a temperature near the reaction temperature by heat exchange with the temperature control iluid in jacket .1I or they are preheated in the lower part of reactor 10 by contact with hot catalyst circulating from an upper part of the reaction zone.

In the apparatus of Fig. 2 the temperature con-` trol means provided by Jacket 1i and the temperature control fluid therein are provided to illustrate the use of this method of removing the heat of reaction in combination with the direct injection of yaporizable cooling fluid through nozzles 84, Bl' and 86. Furthermore in the relatively small scale apparatus of Fig. 2 the use of Jacket 'H and the liquid contained therein is helpful in simulating the conditions which exist in a 'much larger commercial installation. In the single 'tube apparatus of the size shown in Fig. 2 the ratio of radiating surface to volume of the reaction zone is much higher than would be the case in a large installation. Consequently Jacket 1| is helpful in keeping the radiation losses of the apparatus equivalent to those which would be encountered in a larger apparatus. Heating means, not shown, are provided to heat the liquid in jacket 'H to any desired tempera ture.

The reaction mixture is passed in to the apparatus of Fig. 2 through pipe 'I3 at a velocity such that the catalyst is lifted out of pipe 13 and maintained in suspension in reactor 10. valve, not shown, is provided in pipe 13 to prevent catalyst from dropping completely out of the reactor when the gas stream is not being introduced through pipe 13. The gas stream is passed A ball check into pipe 'I3 at a velocity eilective'to aerate .the catalyst mass in reactor." and suspend itin the gas stream therein. In the conditions described generally above, in which the.` lower partof the reactor is occupied by the dense phase of the iluidized catalyst mass and in which the upper Dart of the vreactcr is occupied .by the diffuse phase, the lower boundary of the suspended catalyst mass is located somewhere between the upper and lower boundary of conical member 14. The upper boundary of the dense phase of the catalyst vmass is determined by the ysuperficial velocity of the gas stream and the quantity of catalyst charged to the reactor.

Example I A catalystfor promoting the reaction of cat bon monoxide with hydrogen was prepared as follows: 10,000 grams of cobalt nitrate,

C0 (N Oa) 2.6H2O

andv1910 grams of magnesium nitrate,

Mg(NO3)2.6H2O

were dissolved inlitersl of treated water. 6100 grams of sodium carbonate, NaaCOs.H2O, were dissolved in 50 liters of treated water. Both solutions were heated to the boiling point and the nitrate solution was then added to the carbonate solution with continuous stirring. After the resulting mixture had been stirred thoroughly 4,000 grams oi Super Filtrol" (previously dried at 900 F. for 1.5 hours) at a temperature of 210 F. were added to the solution with vigorous stirring. Aiter thorough stirring the resulting mixture was then i'lltered under a pressure of 30 pounds per square inch. The iilter cake was washed in the filter with 160 gallons of treated water at 180n F. The washedrfilter cake was dried overnight at room temperature by means of a blower. The partially dried material was dried at 210 F. to a moisture content of about 54% and was then extruded through inch dies. The extruded material was then dried overnight at 210 F. to obtain a product having a moisture content of about 16%. This material was then ground to produce a granular mass ilner than 6 mesh but coarser than 20 mesh. The granular material thus produced was reduced in an oven by means of a circulating stream of hydrogen from which water and CO2 were removed constantly. The temperature of the mass of catalyst during this operation was raised to a ilnal temperature of 700 F. during which time the production of water ceased. The reduced catalyst was thengroundin an atmosphere of C02 to a powder ofthe desired size. .The following is a screen analysis of this powder.

Weight This catalyst hadtheffollowing approximate composition in parts by weight: Co:0.15MgO:2.0

.above were introduced while maintainedin an.-

atmosphere of CO2. The catalyst mass was then heated to approximately 400 F. by heating the water bath in jacket 1I. During this time the catalyst was aerated with small streams of CO2 until the temperature reached 300 F. Then hydrogen was used as the aerating medium until the admission of feed gas. After the catalyst mass had been heated to the desired reaction temperature the introduction of preheated feed gas was initiated. Conversion started substantially immediately and the operation was continued for some time during which the temperature was controlled by the water bath in jacket 1I. Then the water was withdrawn from jacket Il and the temperature in the catalyst bed was controlled by the introduction through nozzles L 85 and I6 of a naphtha, produced by the reduction oi' carbon monoxide with hydrogen. boiling between 126 and 360 F., and containing 16.6% mono-oleilns. The connections between conduits 1! and 00 and the recovery system were reversed every minutes and the catalyst filter not in use was blown back by the passage of tail gas therethrough in the reverse direction. The conditions observed and the results obtained during s two periods of this operation are set forth in the following table under columns A and B.

A B C Hours on condition 18 12 30 Operating conditions: o

Average catalyst temperatures, F.-

8 5 it above pipo 73 422 417 389 431 416 398 446 440 406 407 404 410 324 3m 414 268 265 414 Charge gas temperature, F 402 406 414 Pressure (pounds/sq. in.)-Outlet 25 25 Bed conditions- Bed heightin feet 8. 2 8. 0 7. 3 Catalyst density (pounds/cu. it.) 53 54 46 Velocity (it/sec.) at the inlet. 0. 47 0. 44 0. 62 Cu. ft. inlet gas/hn/cn. it. catalyst. S 376 5&5 Liters inlet gas/hL/gram cobalt. l, 4l 1. 30 1. 0 Tt foughputs- Gas efhgering catalyst bed (std.

cu. Gas leaving catalyst bed (std. cu.

t. Blow back gas to filter (std. cu.

The above data indicate that while substantial conversion of the reactants 4occurred with the development of sufllcient heat of reaction to `V`Vrequire the injection of the large amount of cooling liquid indicated the catalyst temperature was maintained within the required degree of uniformity and the fluidized condition of the catalyst was not affected by the liquid iniected into the reactor and vaporized therein. The measure of temperature control is indicated by the small proportion ofthe CO which was converted to methane and ethane while reacting a large proportion of the CO in the charge gas. The low temperature near the bottom of the reactor apparently was caused by heat losses from the lower part of the react..r and pipe 13. The velocity in the foregoing table is based on feed plus vaporized oil injected through pipe 84.

For purposes ofi comparison the results ob'. tained from a similar operation in which temperature was controlled entirely by means of the presence of cooling water in jacket 1I are given in the above table under column C. In the operation represented by column C water under a pressure of 204 pounds per square inch was maintained in Jacket 1i to provide a water bath at a temperature of 389 F. The comparison of the results given in column C with those given in columns A and B indicates that the control of the temperature by direct injection of cooling fluid was as effective as that obtained by indirect heat exchange between the reactor and the surrounding water bath. This indicates the advantage in favor of the direct injection method since it is not dependent upon the use of a reaction zone of small diameter whereas the method represented by column C is dependent upon the use of a small diameter reaction zone as exemplified by reactor 10. That the operations represented by columns A and B provided good control of the reaction temperature is shown by the low conversion of carbon monoxide to methane and ethane obtained in these operations and the relatively uniform temperatures in the dense phase of theucatalyst zone.

Example II A catalyst was prepared in accordance with the following procedure:

A cobalt nitrate solution was prepared by dissolving 10,000 grams of Co(NOa)zO.6H2O in 50 liters of water. A sodium carbonate solution was prepared by dissolving 6,100 grams of NazCOaHnO in liters of water. With both solutions at the boiling point the cobalt nitrate solution was added with stirring to the sodium carbonate solution.

' After thorough stirringv 4,000 grams of dried tained was heated to honing with vigorous stirring. after which the slurry was filtered again. During this operation the filter cake was washed with 300 gallons of hot treated water. The filter cake thus obtained had a water content of approximately 70 weight per cent. This material was partially dried at room temperature to a water content of approximately 57% 'and was then extruded through a inch diameter orlflce. The extruded material was heated overnight in an oven at 420 F. `The material thus obtained was in the form of hard lumps and had a water content of approximately 7.6 weight per cent. This material was then ground in a Braun disc mill and screened to collect material passing through a 40 mesh sieve. Material which did not pass the sieve was recycled to reduce the batch to a size smaller than 40 mesh.

d The following is a screen analysis of this pow- Weight Per Cent After quire the injection of substantial amounts of 17 6.3 pounds of this material was charged to reactor 1I, this amount being chosen to produce 5.8 pounds of catalyst in the reactor after reduction. The unit was flushed out with nitrogen and then hydrogen was passed in through pipe 13.'

Jacket 1i was filled with a suitable temperature control i'iuid such as "Dowtherm and by heating this fluid in the manner described above the temperature of the catalyst mass was gradually raised. After the temperature of the catalyst was raised to 400 F. therate of introduction of hydrogen was increased to 40 cubic feet per hour and the temperature was raised, while operatingy rapidly to 400 F. The flow of the reaction prod-v uct through conduitsv 'i9 and 80 was reversed every l5 minutes and the catalyst filter not in use was blown back by the passage of tail gas water the catalyst temperature was maintained within the required degree of uniformity and the iiuidized condition of the catalyst was not aiTected by the water injected into the reactor and vaporized therein. The measure of temperature control in the operation of column D is indicated bythe small proportion of carbon montherethrough in the reverse direction. This operation was continued for some time, during which the temperature was `controlled by the water bath in jacket 7i. Then the water was removed from the jacket and the temperature in the catalyst bed was controlled by the introduction of water through nozzles il, I5 and 06. The conditions observed and the results obtained during a period'of this operation are set forth in the following table under column D. In column E oi the following table there are set forth the conditions and results of a comparable operation in which temperature control was obtained entirely by means of a water bath in jacket 1I the water bath being held un der a pressure of 307 pounds per square inch to produce a water bath temperature oi' 425 F.

i D i .E

Hours on condition 6 24 Operating conditions:

Average catalyst temperatures, F.-

6.5 feet above pipe 73.---. 420 433 4.5 feet above pipe 73. 435 440 2.5 feet above pipe 73. 427 443 1.5 feet above pipe 73... 424 448 0.5 feet above pipe 73 422 450 (rlhsrgegstem rature .i1 280 77 ressure poun s per square nc Inlet 48 47 Outlet 45 45 Bed conditions Bed height in ieet 5.0 5. 5 Catalyst density (pounds/cu. it.) 54 49 8u cial velocity (iL/sec )l at the inlet 0. 63 75 Cn. r./cu. it. catalyst 970 1,170 Liters inlet gas/hn/gzam cobalt 3. 7 5.0 Throughputs- Gas entering catalyst bed (std. cu. ft.) 573. 3 3,168. 0 Gas leaving catalyst bed (std. cu. it.) 422. l l, DE). 6 Blow back gas to llltcr (std. cu. i'tJhr.) 14. l 10. 4 Ccs. of water injected perhour (at 70 F.)-

Through nozzle 84 2m Through nozzle 85 150 l l! c'lllhrongh niazirzl lli 110 Ana o arge gas rec Pilicent C0; 3. 3 3. Per contl C0 25. 3 30. Per cent Hs 66. 4 y 6l. Per cent CHri-N 4. 2 4. Plc; cent H;0- 0. 8 0. Per cent C0 reacted 33 Per cent C0 converted to methane and ethane. 3.0 ll

The above data indicate that while substantial conversion of the reactants occurred with the,

development of snmcient heat of reaction to remonroe eco oxide which was converted to methane and ethane and by the uniform temperatures in the catalyst bed. 4

In the operations of Examples I and II the coutrol of the temperature of the catalyst mass, in the operations exemplifying the invention, was eilected entirely by the injection of cooling fluid which was either naphtha or water. While this method of ytemperature control has been shown to be sumcieht the invention includes within its scope also the use of the liquid injection method of temperature control in combination with other' control methods such.as indirect heat exchange of cooling fluid with the catalyst mass. The latter method of operation is villustrated by the following example involving operations in which the rreactor 1l was surrounded by a water bath in 'jacket 1i and in which cooling was eilected by the injection of a suillcient quantity of water to absorb the exothermic heat of the reaction as sensible heat and as heat of vaporization.

Example m The same catalyst used in Example II was employed in this example. However, in the operation represented by column D of Example II 1 -jacket 1| was empty whereas in this example jacket 1i contained water maintained under a pressure equivalent to a temperature of 426 F. The operating conditions and results obtained in selected periods from two separate operations of this general nature are set forth in the following table:

Hours on condition 12 6 Operating conditions:

Average catalyst temperatures, F.-

6.5 feet above pipe 73 433 431 4.5 feet above pipe 73... 436 432 2.5 feet above pipe 73... 430 430 1.5 feet above pipe 73-.. 319 302 0.5 feet above pupe 73 414 310 Charge gas temperature 73 70 Pressure (pounds per square inch) In t 48. 5 47. 5 Outlet 45.0 44.6

conditions- Bed height in feet 5. 0 5. o Catalyst density (pounds/cu. it.). 53 54 Superilcial velocity (it/sec.) at the 0. 07 0. 61 Cu. it. inlet gas/hL/cu. i t. catalyst. 935 981 Liters inlet gas/hr./gram cobalt 3. 67 3. 71 Tluoughputs-` Gas entering catalyst bed (std. cu. ft.)... 1,151. 6 582.6 Gas leaving catalyst bed (std. cu. it.) 767. 3 370. B Blow back gas to illter (std. cu. it./hr.) 17.0 25. 6 Ccs. of water injected per hou (at 70 F.)

Through nozzle 84 662 Through nozzle 85... 0 706 Through nozzle 86 0 v Analysis oi Charge gas (air and H10 iree):

Per cent CO, 4. i 2.0 Percent C0 30.0 28. 5 Per cent EL 60.8 65. 2 Per cent CH. 4.0 4.0 `Per cent Nl 1.1 0.3 Results:

Per cent C0 reacted 32.1 4i. 6 Per cent' C0 converted to methane and ethane. 2.0 10.4

Satisfactory control of the reaction vtempera.-

ture in the operations represented by columns F- and G of the foregoing table is indicated by the direct temperature measurements in the reactor and by the low percentage of the carbon monoxide feed which was converted to methane and 19 ethane. It will be noted that in the operation represented by column F all of the water was injected through nozzle Il near the bottom ofthe reactor whereas in the operation of column G' type which would be employed in commercial practice. Consequently the operations ot col'- umns F and G, in so far as temperature controlAv is concerned, simulate the conditions which would be encountered in commercial practice.

The invention has been illustrated by. reference to the use of reactors oi large cross-sectional area containing a single mass of catalyst 4and by-reference to the use of reactors in which-the. catalyst mass is contained in one or kmore off a plurality.

of tubes of relatively small cross-sectionalzarea; Thefilrst type of reactor is exemplified by reactor Il of Fig. 1 andthe second type of reactor is exemplined by Fig. 2. It will be understood that while the reactor of Fig, 2 Vis limited to a single tube, because of limitations on thesize of apparatus ior experimental use, the principles ofoperation illustrated thereby are directly applicable to a larger reactor made up of a plurality of tubes of the same or larger diameter in a common zonel inwhich they may be in contact with a water bath in addition to being cooled by direct injectionor in which they may be cooledentirely by the latter method.

While the tubular type of reactor exempliiled by Fig. 2 may appear to involve the use of a catalyst mass of relatively small cross-sectional area the diameter oi the tube comprising reactor 'IQ' in Fig. 2 is, nevertheless, substantially greater than tubes in tubular reactors employing a ilxed catalyst bed. In the latter ,the maximum diameter of the tubes is approximately V4 that of reactor 10 whereby the tubes employed have a cross sectional area of` approximately that of reactor 10.

The cooling fluid which is injected into the reactor and into contact with the catalyst mass preferably is distributed in the reactor zone in a manner to permit substantially instantaneous vaporization of the liquid and prevent the accumulation of liquid inany part of the reaction mass. The latter result is undesirable since it may cause an agglomeration of catalyst particles into large masses whereby the fiuidized nature of the catalyst mass would be impaired. In a reaction zone of large cross sectional area in which the catalyst circulates at a rapid rate throughout the reaction zone the distribution of the cool liquid in the reaction zone is carried out largely by the catalyst itself. On the other hand in reactors in relatively small cross-sectional areas such as Fig. 2, in which vertical circulation of catalyst is less effective it is more important to provide for proper distribution of cooling iluid by injection at a plurality of points as illustrated.

I claim:

l. A process for hydrogenating carbon oxides which comprises continuously ilowing ag'aseous mixture comprising hydrogen and a carbon oxide 20 upwardly in a reaction zone throughs. mass of nnely divided contact material comprising a catalyst for the reaction and at the reaction temperature to maintain the body of contact material substantially in suspension, limiting the upward velocity: of the gaseous mixture to maintain the greater part of the mass of contact material in a relatively dense pseudo-liquid phase, maintain'- i ing the upward velocity of the gaseous mixture higher than the iree settling rate of particles comprising a substantial proportion of said dense phase-whereby there isproduced highly turbulent motion-of the particles of contact material in the dense phase in which the particles circulate throughout .the dense phase at a high rate to promote;uniformtemperature conditions throughout the dense phase, providing a contact mass of sumcient bulk to produce a dense phase deep enough toaiiorda'length of timeV of contact be tween the'gaseous reactants and catalyst in the dense-phase sumcient to react a substantial proportion ot said carbon oxide with hydrogen, withdrawing said gaseous mixture irom said reaction zone after passage thereof through said dense phase. treating said withdrawn gaseous mixture to-separate therefrom a liquid containing iinely divided contactmaterial carried from the reaction zonefbyentralnment in said withdrawn gaseous mixture, and returning liquid containing catalyst thus recovered -tossaid' reaction zone.

2. A- process i'or hydrogenating carbon oxides which-comprises continuously flowing a gaseous mixture comprising-hydrogen and acarbon oxide upwardly in areaction zone through a mass of nely dividedoontact'material comprising a catalyst. for the reaction and at thereaction tern peraturerto maintain the body of contact material substantially' in-suspension, limiting the up- 'ward velocity ofthe gaseous mixture to maintain the-greater part o! the mass of contact material in.a relatively dense pseudo-liquid phase, maintaining the upward velocity of the gaseous mixture higher than-the tree settling rate of particles comprising a substantial proportion of said dense phase whereby there is produced highly turbulent motion of the particles of contact material in the dense phase in which the particles circulate in the dense phase at a high rate to promote uniform temperature conditions in the dense phase, providing a contact mass of sumcient bulk to produce a dense phase deep enough to aiiord a length of time of contact between the gaseous reactants and catalyst in the dense phase sumcient to react a substantial proportion of said carbon oxide with hydrogen, withdrawing said gaseous mixture from said reaction sone after passage thereof through said dense phase, treating said withdrawn gaseous mixture to separate therefrom a liquid containing finely divided contact material carried from the reaction zone by entrainment in said withdrawn gaseous mixture, separating catalyst from said liquid fraction, forming said separated catalyst into a slurry with a liquid which is completely vaporizable under the reaction conditions, and directly injecting said slurry into said reactor to eilect vaporization of the liquid component of said slurry and commingling of the catalyst component with the said dense phase.

3. A process for hydrogenating carbon oxides which comprises continuously ilowing a gaseous mixture comprising hydrogen and a carbon oxide upwardly in a reaction zone through a mass of ilnely divided contact material comprising a catalyst for the reaction and at the reaction temtain the greater part of the mass of contact material in a relatively dense pseudo-liquid phase, maintaining the upwardv velocity of the gaseous mixture higher "than the free settlingv rate of particles comprising a substantial proportion of said dense phase whereby there is produced highly turbulent motion of the particles of contact material in the dense phase in which the particles circulate in the dense phase at a high rate to promote uniform temperature conditions in the dense phase, providing a contact mass of sumcient bulk to produce a, dense phase deep enough to afford a length of time of contact between the gaseous reactants and catalyst in the dense phase suilicient to react a substantial proportion of said carbon oxide with hydrogen, withdrawing said gaseous mixture from said reaction zone after passage thereof through said dense phase, treating said gaseous mixture to separate therefrom a relatively high boiling liquid fraction containing ilnely divided contact material carried from the reaction zone by entrainment in said gaseous mixture and a lower boiling liquid fraction completely vaporizable under the re- 22 action conditions, separating catalyst from said high boiling fraction, forming said separated catalyst into a slurry with at least a portion of said ylow boiling liquid fraction, and injectng the slurry thus formed directly into the reaction zone to eiect vaporization of the liquid` component of sa-id slurry and commingling of the catalyst component of said slurry with said dense phase.

LOUIS C. RUBIN.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS 

